Hydrate film growth has been examined at the hydrocarbon/water interface for cyclopentane and methane hydrate. Video microscopy was used to measure hydrate film thickness, propagation rate across the hydrocarbon/water interface and gas consumption measurements characterized the hydrate formation mechanism. Cyclopentane and methane hydrate film formation were measured over the temperature range of 260–279K and pressure range of atmospheric to 8.3MPa. Hydrate formation was initiated by the propagation of a thin, porous film across the hydrocarbon/water interface. The propagation rate and thickening of the hydrate film was strongly dependent on the hydrate former solubility in the aqueous phase, in the absence and presence of hydrate. Cyclopentane hydrate film thickness began at ~12 μm and grew to a final thickness (15–40 μm) which increased with subcooling. Methane hydrate film thickness began at ~ 5 μm and grew to a final thickness (20–100 μm) which also increased with subcooling. The hydrate film grew into the water phase. Gas consumption measurements indicated that the aqueous phase supplied hydrate former during the initial hydrate growth, and the free gas supplied the hydrate former for film thickening and development. Hydrate film formation at the hydrocarbon/water interface was proposed to consist of three consecutive stages: propagation, development and bulk conversion.

Raman spectroscopic measurements of various hydrogen bearing clathrate hydrates have been performed under high (< 1cm-1) and low resolution (>2 cm-1) conditions. Raman bands for hydrogen in most common clathrate hydrate cavities have been assigned. Unlike most clathrate hydrate guests, the general observation is no longer valid that the larger the clathrate cavity in which a guest resides, the lower the vibrational frequency. This is rationalized by the multiple hydrogen occupancies in larger clathrate cavities. Both the roton and vibron bands for hydrogen clathrates illuminate interesting quantum dynamics of the enclathrated hydrogen molecules. At 77K, the progression from ortho to para H2 occurs over a relatively slow time period (days). The para contribution to the roton region of the spectrum exhibits the triplet splitting also observed in solid para H2. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature and with isotopic substitution by deuterium. Raman spectra from H2 and D2 hydrates suggest that the occupancy patterns between the two hydrates are analogous. The Raman measurements demonstrate that this is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

Large amounts of CH4 in the form of solid hydrates are stored on continental margins and in permafrost regions. If these CH4 hydrates could be converted into CO2 hydrates, they would serve double duty as CH4 sources and CO2 storage sites. Herein, we report the swapping phenomena between global warming gas and various structures of natural gas hydrate including sI, sII, and sH through 13C solid-state nuclear magnetic resonance, and FT-Raman spectrometer. The present outcome of 85% CH4 recovery rate in sI CH4 hydrate achieved by the direct use of binary N2 + CO2 guests is quite surprising when compared with the rate of 64 % for a pure CO2 guest attained in the previous approach. The direct use of a mixture of N2 + CO2 eliminates the requirement of a CO2 separation/purification process. In addition, the simultaneously-occurring dual mechanism of CO2 sequestration and CH4 recovery is expected to provide the physicochemical background required for developing a promising large-scale approach with economic feasibility. In the case of sII and sH CH4 hydrates, we observe a spontaneous structure transition to sI during the replacement and a cage-specific distribution of guest molecules. A significant change of the lattice dimension due to structure transformation induces a relative number of small cage sites to reduce, resulting in the considerable increase of CH4 recovery rate. The mutually interactive pattern of targeted guest-cage conjugates possesses important implications on the diverse hydratebased inclusion phenomena as clearly illustrated in the swapping process between CO2 stream and complex CH4 hydrate structure.

Evaluation of host geologic sediment interactions with carbon dioxide is very important in sequestration strategies. The objective of the study is to experimentally investigate the effects of different soil mineral types on carbon dioxide hydrate formation. At isothermal, isochoric, and isobaric conditions, batch experiments were conducted with different types of solids (bentonite, kaolinite, nontronite, pyrite, and soil) and electrolytes (NaCl, KCl, CaCl2, and MgCl2) to measure carbon dioxide hydrate formation times. A 50 mL pressurized vessel was used for the experiment by bubbling gaseous CO2 into the solid suspension. We observed that the formation time of carbon dioxide hydrate was dependent on the reactor temperature (273.4 K and 277.1 K) and types of solid and electrolyte. A clear peak was observed in the temperature profile of each experimental run and determined as the hydrate formation time. This is due to the initiation of the hydrate crystallization and latent heat release at the hydrate formation time. The temperature profiles vary significantly with respect to the types of solids and electrolytes. As crystallization initiates, peaks were observed at higher temperatures in pyrite and soil suspensions. The results showed that hydrate formation times for clay minerals in water were approximately twice and 10 times faster than that for pyrite and soil, respectively. The rates of gas consumption were able to be determined by the pressure monitoring. The kaolinite appeared to have the fastest gas consumption rate among the clay mineral suspensions, which was 2.4 times and 7.4 times faster than nontronite and bentonite, respectively. Results from these experiments seem to provide an insight on the formation and growth of carbon dioxide hydrate, once sequestered into the sea bed sediments under the deep sea environment.

A HP micro DSC-VII from SETARAM was used to study the efficiency and mechanism of action of commercial kinetic inhibitors for gas-hydrate formation in drilling fluids (OBM). The main objective was to find a suitable and reliable method of screening for these chemicals. The DSC technique consists in monitoring the heat exchanges, due to phase changes (here hydrate formation or dissociation), either versus time at constant temperature or versus temperature during a heating or cooling program. All products showed a gas hydrate dissociation temperature (at a given pressure) that matched with theoretical and previously published data. Nevertheless, for some additives two thermal signals were observed on the thermograms, one that corresponds to the theoretical value and another at a higher temperature (about +4°C). This second peak is insensitive to the heating rate applied for the dissociation, but the areas ratio (1stpeak/2nd peak) changes with the additive concentration and with the driving force applied during the hydrate formation. Additionally, additive/water and additive/water/THF systems were tested. In each case, two dissociation peaks were also measured. The results allow us to disregard any kinetic effects bonded to this thermal phenomenon, and lead us to infer that some additives may induce non-classical crystalline structures of gas hydrates. To verify these results, crystallographic and spectroscopic experiments must be performed. The stabilities of these new compounds are under study.

Simulation of the system behavior of hydrate-bearing geologic media involves solving fully coupled mass- and heat-balance equations. In this study, we develop a domain decomposition approach for large-scale gas hydrate simulations with coarse-granularity parallel computation. This approach partitions a simulation domain into small subdomains. The full model domain, consisting of discrete subdomains, is still simulated simultaneously by using multiple processes/processors. Each processor is dedicated to following tasks of the partitioned subdomain: updating thermophysical properties, assembling mass- and energy-balance equations, solving linear equation systems, and performing various other local computations. The linearized equation systems are solved in parallel with a parallel linear solver, using an efficient interprocess communication scheme. This new domain decomposition approach has been implemented into the TOUGH+HYDRATE code and has demonstrated excellent speedup and good scalability. In this paper, we will demonstrate applications for the new approach in simulating field-scale models for gas production from gas-hydrate deposits.

The liquid-to-crystal nucleation temperature is measured for clathrate-forming mixtures of tetrahydrofuran and water using both an automatic lag time apparatus (ALTA) and a ball screening apparatus. Our results are conclusive evidence that no so-called “memory effect” exists. Either the solid form melts fully or it does not. If it does not, then no supercooling is possible on the next cooling down of that sample, and if it does then the second cooling run and freezing on a sample is just as likely to have a colder nucleation temperature as a hotter one.

The statistics of liquid-to-crystal nucleation are measured for clathrate-forming mixtures of tetrahydrofuran and water using an automatic lag time apparatus (ALTA). We measure the nucleation temperature where a single sample is repeatedly cooled, nucleated and thawed. This is done for a series of tetrahydrofuran concentrations and in several different sample tubes since the nucleation is heterogeneous and occurring on the tube wall. The measurements are also done at the same concentrations and tubes but with an added catalyst, a single crystal of silver iodide. We discuss the need for this type of measurement if the true nucleation temperature of the clathrate is to be found. Comparisons are also made with our high pressure data on real-world clathrate formers.

Hundreds of pockmarks and mounds, which seismic reflection sections show to be underlain by chimney-like structures, exist in southeast part of the Vøring plateau, Norwegian continental margin. These chimneys may be representative of a class of feature of global importance for the escape of methane from beneath continental margins and for the provision of a habitat for the communities of chemosynthetic biota. Thinning of the time intervals between reflectors in the flanks of chimneys, observed on several high-resolution seismic sections, could be caused by the presence of higher velocity material such as hydrate or authigenic carbonate, which is abundant at the seabed in pockmarks in this area. Evidence for the presence of hydrate was obtained from cores at five locations visited by the Professor Logachev during TTR Cruise 16, Leg 3 in 2006. Two of these pockmarks, each about 300-m wide with active seeps within them, were the sites of high-resolution seismic experiments employing arrays of 4-component OBS (Ocean-Bottom Seismic recorders) with approximately 100-m separation to investigate the 3D variation in their structure and properties. Shot lines at 50-m spacing, run with mini-GI guns fired at 8-m intervals, provided dense seismic coverage of the sub-seabed structure. These were supplemented by MAK deep-tow 5-kHz profiles to provide very high-resolution detail of features within the top 1-40 m sub-seabed. Travel-time tomography has been used to detail the variation in Vp and Vs within and around the chimneys. Locally high-amplitude reflectors of negative polarity in the flanks of chimneys and scattering and attenuation within the interiors of the chimneys may be caused by the presence of free gas within the hydrate stability field. A large zone of free gas beneath the hydrate stability field, apparently feeding several pockmarks, is indicated by attenuation and velocity pull-down of reflectors.

While alternative natural gas transportation technologies against currently available pipeline or liquefied natural gas (LNG) are expected to develop to be suitable for small and medium or remote gas fields, Mitsui Engineering & Shipbuilding Co., Ltd. (MES) has been studying natural gas hydrate (NGH) transportation chain and advocated at ICGH2005 the NGH chain was economical compared with conventional LNG system under some conditions. Meanwhile, MES has been carrying out research and development on the relevant technology development including construction of 600 kg/day class NGH production and pelletizing plants and a re-gasification facility and the process technology resulted from this R&D leads to the forthcoming demonstration plant of 5 ton/day production (under construction) to be dedicated to the demonstration project of small-lot NGH land transportation in western Japan. As the latest achievement, MES and Mitsui & Co., Ltd. (Mitsui) established NGH Japan Co., Ltd. (NGHJ) in April 2007, in order to study in detail on actual viability of NGH ocean transportation chain. NGHJ, MES and Mitsui have been conducting a practical feasibility study on certain cases in Southeast Asia in cooperation with 6 Japanese leading companies related to natural gas businesses. The study suggests that NGH chain was appropriate as a media for transportation from Southeast Asia to Japan and regional transportation within Southeast Asia in view of economics.